Modelling spills of water-reactive chemicals

This paper describes part of a programme of work undertaken at the Health and Safety Laboratory (HSL) to investigate the behaviour of selected water-reactive chemicals. Following an accidental release, such substances react exothermically with any water present, generating acidic vapours. The STAWaRS (Source Term Assessment of Water Reactive Substances) software was developed for the Health and Safety Executive (HSE) by ESR Technology to model this complex process. The aims of the study described here were to provide experimental validation of the heats of hydrolysis used within STAWaRS, and to perform sensitivity studies on selected STAWaRS input parameters.The heat of hydrolysis of acetyl chloride was measured and showed good correlation with the value used within STAWaRS. Some of the variables that influence the severity of acetyl chloride spills are examined, with reference to predictions made by the STAWaRS model. The heats of hydrolysis of titanium tetrachloride previously measured at HSL are also discussed, and the effect of adopting these experimentally derived values for modelling spills is shown for a hypothetical land use planning case. This study demonstrates the importance of using experimentally validated values for STAWaRS input parameters.     

Effects of significant damage of flame gap surfaces in flameproof electrical apparatus on flame gap efficiency

Electrical apparatus for use in the presence of explosive gas atmospheres has to be specially designed to prevent the apparatus from igniting the gas. Flameproof design is one of several options, and one requirement is then that any holes and slits in the enclosure wall be designed to prevent a possible gas explosion inside the enclosure from being transmitted to an explosive gas cloud outside it. Current standards (IEC) require that joint surfaces have a surface roughness of <6.3 μm. Any damaged joint surface has be restored to this quality. The present investigation has demonstrated that flame gap surfaces in flameproof electrical apparatuses can suffer considerable mechanical and corrosive damage before the flame gaps no longer function satisfactorily. In some cases very significant mechanical surface damage in fact improves the gap performance. This indicates that current high costs of repairing and replacing flameproof electrical apparatus in process plants offshore and onshore can be reduced considerably without any increase of the explosion risk.     

On the development of a new hybrid risk assessment process using occupational accidents’ data: Application on the Greek Public Electric Power Provider

The occupational accidents have a major impact upon human integrity and also bring about high costs for the social health and insurance system of a country. In addition, risk analysis is an essential process for the safety policy of a company, having as main aim the effacement of any potential of damage in a productive procedure, while the quantified risk evaluation is the most crucial part of the whole procedure of assessing hazards in the work. The main goal of this study is double: a) the development and presentation of a new hybrid risk assessment process (HRAP) and b) the application of HRAP in the Greek Public Power Corporation (PPC) (the unique electric power provider and the largest industry in Greece), by using occupational accidents that have been recorded, during the 12-year period of 1993-2004. The new process consists of four distinct phases a) the hazard sources’ identification phase, b) the risk consideration phase, c) the risk-evaluation phase, and d) the phase of the risk assessment and safety-related decision making. The results show that in some cases the risk value has been calculated in PPC to be higher than 500 (in the risk rating of 0-1000), which imposes the taking of suppressive measures for abolishing the danger source, while the fatal accident frequency rate (per 10⁸ man-hrs) is FAFR ≅ 2.4.     

Person–organization and person–supervisor fits: Employee commitments in a Chinese context

The present study simultaneously examined people's perceptions of person–organization (PO) and person–supervisor (PS) fit and related these perceptions to employees' commitments. Three‐hundred‐and‐sixty employee–supervisor dyads from Taiwanese organizations reported about their PO fit and PS fit perceptions. In addition, supervisors reported about their perceptions of fit and guanxi with each of their employees. Results indicated that PO and PS fit perceptions both had an independent and additive relationship with organizational commitment. The link between employee PS fit perceptions and organizational commitment was mediated by commitment to the supervisor. Both employee and supervisor fit perceptions contributed to commitment to the supervisor through their influence on the quality of the leader‐member exchange (LMX). Guanxi could not explain additional variance in LMX and supervisor commitment. Implications for theory and practices regarding person–environment fit, commitment, and LMX are discussed. The study findings offered suggestions for a new Theory of Multiple Fits. Copyright © 2010 John Wiley & Sons, Ltd.     

Prediction of the confidence interval for stability analysis of chain pillars in coal mines

The conventional deterministic approach based (DAB) methods are simple and widely used to determine an adequate chain pillar size in coal mines where geological settings, coal characterizations and mining methods have been explored. It is evident that such deterministic methods have some intrinsic limitations in handling uncertainties in material properties, non-regular geometries and different mining operations. In the deterministic stability analysis of a chain pillar, the safety factors as well as all input parameters are deterministic. Although, these parameters generally exhibit uncertainty and should lead to a probabilistic expression for the safety factor. The probabilistic analysis provides a confidence interval to express the reliability of chain pillars stability.In this paper, safety factor is defined as a probabilistic function and the failure probability of designed chain pillar of Tabas coal mine is then evaluated using the First Order Second Moment (FOSM) and the Advanced Second Moment (ASM) methods. The results of the probabilistic stability analysis show that the confidence interval for designed pillars with both mentioned methods applied are similar and their values vary from 84% to 88%. The results of such analyses can be used as a basis for decision-making about the size of chain pillars and reduce the risk of pillars stability as well as the uncertainties. However, a trade-off between cost is essential for making the final decision.     

Flammability of hydrocarbon and carbon dioxide mixtures

The effect of carbon dioxide (CO₂) concentration on the ignition behaviour of hydrocarbon and CO₂ gas mixtures is examined in both jets and confined explosions. Results from explosion tests are presented using a 20 l explosion sphere and an 8 m long section of 1.04 m diameter pipeline. Experiments to assess the flame stability and ignition probability in free-jets are reported for a range of different release velocities. An empirically-based flammability factor model for free-jets is also presented and results are compared to ignition probability measurements previously reported in the literature and those resulting from the present tests.The results help to understand how CO₂ changes the severity of fires and explosions resulting from hydrocarbon releases. They also demonstrate that it is possible to ignite gas mixtures when the mean concentration is outside the flammable range. This information may be useful for risk assessments of offshore platforms involved in carbon sequestration or enhanced oil recovery, or in assessing the hazards posed by poorly-inerted hydrocarbon processing plant.     

Bioaccumulation surveillance in Milford Haven Waterway

Biomonitoring of contaminants (metals, organotins, polyaromatic hydrocarbons (PAHs), PCBs) was undertaken in Milford Haven Waterway (MHW) and a reference site in the Tywi Estuary (St Ishmael/Ferryside) during 2007–2008. Bioindicator species encompassed various uptake routes—Fucus vesiculosus (dissolved contaminants); Littorina littorea (grazer); Mytilus edulis and Cerastoderma edule (suspension feeders); and Hediste (=Nereis) diversicolor (sediments). Differences in feeding and habitat preference have subtle implications for bioaccumulation trends though, with few exceptions, contaminant burdens in MHW were higher than the Tywi reference site, reflecting inputs. Elevated metal concentrations were observed at some MHW sites, whilst As and Se (molluscs and seaweed) were consistently at the higher end of the UK range. However, for most metals, distributions in MH biota were not exceptional. Several metal-species combinations indicated increases in bioavailability upstream, which may reflect the influence of geogenic/land-based sources—perhaps enhanced by lower salinity. TBT levels in MH mussels were below OSPAR toxicity thresholds and in the Tywi were close to zero. Phenyltins were not accumulated appreciably in M. edulis, whereas some H. diversicolor populations appear subjected to localized (historical) sources. PAHs in H. diversicolor were distributed evenly across most of MHW, although acenaphthene, fluoranthene, pyrene, benzo(a)anthracene and chrysene were highest at one site near the mouth; naphthalenes in H. diversicolor were enriched in the mid-upper Haven (a pattern seen in M. edulis for most PAHs). Whilst PAH (and PCB) concentrations in MH mussels were mostly above reference and OSPAR backgrounds, they are unlikely to exceed ecotoxicological thresholds. Bivalve Condition indices (CI) were highest at the Tywi reference site and at the seaward end of MH, decreasing upstream—giving rise to several significant (negative) relationships between CI and body burdens. Despite the possible influence of salinity gradient as a complicating factor, multivariate analysis indicated that a combination of contaminants could influence the pattern in condition (and the biomarkers metallothionein and TOSC). Integrating bioaccumulation data with biological and biochemical endpoints is seen as a useful way to discriminate environmental quality of moderately contaminated areas such as MHW and to prioritise cause and effect investigations.     

Mixed response in bacterial and biochemical variables to simulated sand mining in placer-rich beach sediments,Ratnagiri, West coast of India

We investigated the influence on bacterial community and biochemical variables through mechanical disturbance of sediment-akin to small-scale mining in Kalbadevi beach, Ratnagiri, a placer-rich beach ecosystem which is a potential mining site. Changes were investigated by comparing three periods, namely phase I before disturbance, phase II just after disturbance, and phase III 24 h after disturbance as the bacterial generation time is ≤7 h. Cores from dune, berm, high-, mid-, and low-tide were examined for changes in distribution of total bacterial abundance, total direct viability (counts under aerobic and anaerobic conditions), culturability and biochemical parameters up to 40 cm depth. Results showed that bacterial abundance decreased by an order from 10⁶ cells g^− 1 sediment, while, viability reduced marginally. Culturability on different-strength nutrient broth increased by 155% during phase II. Changes in sedimentary proteins, carbohydrates, and lipids were marked at berm and dune and masked at other levels by tidal influence. Sedimentary ATP reduced drastically. During phase III, Pearson’s correlation between these variables evolved from non-significant to significant level. Thus, simulated disturbance had a mixed effect on bacterial and biochemical variables of the sediments. It had a negative impact on bacterial abundance, viability and ATP but positive impact on culturability. Viability, culturability, and ATP could act as important indicators reflecting the disturbance in the system at short time intervals. Culturability, which improved by an order, could perhaps be a fraction that contributes to restoration of the system at bacterial level. This baseline information about the potential mining site could help in developing rational approach towards sustainable harnessing of resources with minimum damage to the ecosystem.     

Measurement of the proximity effect for indoor air pollutant sources in two homes

Personal exposure to air pollutants can be substantially higher in close proximity to an active source due to non-instantaneous mixing of emissions. The research presented in this paper quantifies this proximity effect for a non-buoyant source in 2 naturally ventilated homes in Northern California (CA), assessing its spatial and temporal variation and the influence of factors such as ventilation rate on its magnitude. To quantify how proximity to residential sources of indoor air pollutants affects human exposure, we performed 16 separate monitoring experiments in the living rooms of two detached single-family homes. CO (as a tracer gas) was released from a point source in the center of the room at a controlled emission rate for 5-12 h per experiment, while an array of 30-37 real-time monitors simultaneously measured CO concentrations with 15 s time resolution at radial distances ranging from 0.25-5 m under a range of ventilation conditions. Concentrations measured in close proximity (within 1 m) to the source were highly variable, with 5 min averages that typically varied by >100-fold. This variability was due to short-duration (<1 min) pollutant concentration peaks ("microplumes") that were frequently recorded in close proximity to the source. We decomposed the random microplume component from the total concentrations by subtracting predicted concentrations that assumed uniform, instantaneous mixing within the room and found that these microplumes can be modeled using a 3-parameter lognormal distribution. Average concentrations measured within 0.25 m of the source were 6-20 times as high as the predicted well-mixed concentrations.